JPS58159438A - Herbicidal compound and composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic compound having biological activity, and in particular to an organic compound having the property of weeding and inhibiting phase growth, a method for producing the compound, and a method for producing the compound. The present invention relates to intermediates and herbicide compositions which are unnecessary for the production of Rubis and methods of using the compound, as well as methods of using the compound and its composition.

The use of certain cyclohexane-1,3-dione conductors as herbicides is known in the art. For example, “Insecticide Handbook J (edited by CR Worth-ing,
British Crop Protection Conference, 6th edition 1979) alloxydim-
cyclohexane-1,3-noon, commercially known as sodium (methyl 3-(1-allylmeximinobutyl)-4-hydroxy-6,6-nomethyl-2-oxenecyclohextuc-3-ene-carboxylate) Its use as a conductor and herbicide is described. This compound has been described in Australian Patent No. 464,655 and in British Patent No. 1,461,170 and US Pat. No. 3,950,420.
No.

More recently, the 1980 British Crop Protection Conference (r1980
2019 UK Crop Protection Conference - Weeds, Proceedings Volume 1, Research Report J
p, 39-46. British Crop Protection Council, 1980), NP55 (2-(N-ethoxybutrimidoyl)-
5-(2-ethylthiopropyl)-3-hydroxy-2
A new herbicide code, cyclohexane-1,3-dione, has been announced. This combination is Australian patent application number A
V-AI-35314/78 and its equivalents.

As above, alloxitum-sodium and NP55
Both are herbicides, that is, herbicides that selectively suppress the growth of weeds (monocots) in broad-leaved crops (dicots).

4th Pesticide Science Conference of the Universal Union of Pure and Applied Sciences in 1978 ("Advances in Pesticide Science - Part 2 Jpp23
5-243. In a paper discussing the chemical structure and herbicide activity of alloxydim-sodium (Pergamon Press, 1979), Iwataki and Hirono
The following disclosure was made regarding the herbicidal selectivity of phenyl-substituted cyclohexane-1,3-dione conductors between wheat and oats.

[When a substituted phenyl group is introduced at the C-5 position (Table 6), Avenafatua
Selectivity between wheat and oats such as Avena 5ativa and Avena 5ativa was observed.

The selectivity was found only in the case of bara-substitution in the phenyl nucleus, the effect was not found in the case of no- or tri-substitution. Even in rose-substitution, the activity or selectivity differed by 8 degrees. The best results were obtained when the methyl group was placed in the free position, and hydroxy or methoxy derivatives gave reasonably good results. ” Novel 5-aryl substituted cyclohexane-1,
It has now been shown that 3-dione conductors exhibit particularly useful cereal selective herbicidal and plant growth regulating activities.

Accordingly, the present invention relates to formula I: where W may be the same or different and is selected from the group consisting of 01-C6 alkyl, C2-C6 alkenyl and C2-C6 alkynyl; , Halodan; Nitro;
Cyano; C1-C6 alkyl; C4- substituted with a substituent selected from the group consisting of halodane, nitro, hydroxy, C1-C6 alkoxy MUC1-C6 alkylthio
C6 alkyl; C2-C6 alkenyloxy; C2-C
6 alkynyloxy; C2-C6 alkanoyloxy;
(C1-C6 alkoxy)carbonyl; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C
6alkylsulfonyl; sulfamoyl; N-(C1~
C6 alkyl) sulfamoyl; N, N-cy(C1-C
6 alkyl) sulfamoyl; benoloxy; benzene ring chalogen, nitro, C1-C6 alkyl, C1-
Substituted benoloxy substituted with 1 to 3 substituents selected from the group consisting of C6 alkoxy and C, to C6 haloalkyl; R8 and R9 are hydrogen, C1 to C6 alkyl, C2 to C6 alkanoyl, benzoyl and the groups NRR independently selected from the group consisting of benol, formyl and C2-C6 alkanoyl and their oximes;
imine and cyanide base derivatives; and the group -(CH2)9- bridging two adjacent carbon atoms of the benzene ring.
and q is an integer selected from 2 to 5; R is hydrogen; C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 alkynyl; the alkyl group is C1 to C6 Alkoxy, 01-C6 alkylthio, phenyl, and benzene 1 selected from the group consisting of halodane, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 alkylthio
Substituted C1-C substituted with a substituent selected from the group consisting of substituted phenyl substituted with 5 to 3 substituents
6 alkyl; C1-C6 (alkyl)sulfonyl; hensensulfonyl; benzene ring cabalokene, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl,
Substituted benzenesulfonyl substituted with 1 to 3 substituents selected from the group consisting of C1-C6 alkoxy and C1-C6 alkylthio; an acyl group; and an inorganic or organic cation; R2 is C4-C6 alkyl; C2-C6 alkenyl; C
2-C6 haloalkenyl; C2-C6 alkynyl; C2
~C6 haloalyanyl; alkyla〃)ノ＼logn, C
1~C6 alkoxy, 01~C6 alkyl, phenyl as well as benzene monkey, rodan, nitro, cyano, C
1-C6 alkyl, C1-C6-10 alkyl, C1-
Directly substituted C1-C6 argyl substituted with a substituent selected from the group consisting of C6 alkoxy and C1-C6 alkylthio, and substituted phenyl directly substituted with 3 substituents. traced from the group consisting of; R3 is sent from the liver consisting of C1-C6 alkyl 41-C6 fluoroalyal C2-C6 alkenyl 4, - C6 alkynyl; p is 0 or 1-4 〃・The number of monkeys who made the land Q is 9;
n is O or Hinoki Teriri arrested from 1 to 3; and m is 0 or V, calculated by the number of bonds released from 1 to 3. ).

In the compound of formula l, X is a group formyl and C2-C
When traced from the 6-alkanoyl kettle to oximes, imines, and their Schiff base derivatives, the properties of oximes, imines, and Schiff base derivatives are not strictly necessary. Although not necessarily bound by theory, in plants the (substituted) imine group is removed so that X is formyl or C2
It appears possible to provide the corresponding compound of formula (1) which is a ~C6 alkanoyl. Formyl group and C2-C6
Suitable values for alkanoyl groups as well as oximes, imines and their Schiff base fermentations are R, hydrogen and C1-C.
5 alkyl, and R1+ is hydrogen, C1 to C6
Alkyl, phenyl, benzyl, hydroxy, 01-C
6 alkoxy, phenoxy and benoloxy, including a group of the formula -〇(R)=NR.

When R1 is derived from acyl in the compound of formula (2), the nature of the acyl group is not strictly i-bag. Although it is often concluded by theory, when R1 is acyl,
It is shown that the acyl group rL can be removed by hydrolysis in plants to give the corresponding compound of formula 1 where R can be removed in aqueous systems.

Suitable acyl groups include alkanoyl, such as C2-C6 alkanoyl; aroyl, such as benzoyl, as well as benzene-kabarodan, nitro, cyano, C1-C6 alkyl,
C1-C6 haloalkyl, 01-C6 alkoxy and C
,~1 piece extruded from the liver consisting of C6 alkylthio~3
Directly substituted benzoyl substituted with 2 substituents; as well as heteroaroyl, such as 2-noroyl, 3-furoyl, 2
-tenoyl and 3-thenoyl;

When R1 in the compounds of formula I is selected from inorganic or organic cations, the nature of the cation is not strictly specific. Although there is no way to connect it by theory,
When R is a cation, it is believed that the cation can be removed in the plant to provide compounds of formula I where R is hydrogen.

A suitable free radical contains alkali and alkaline earth gold parent ions, irrigated metal ions, fluorophore ions, and ammonium ions. Suitable organic cations10.
R', R5a R' and R7ta. Hydrogen: C1-C1
.

Alkyl; alkyl group is hydroxy, halodane and C,
Substituted C, ~C, which is replaced with a substituent derived from the solution consisting of ~C6 alkoxy. Alkyl; phenyl; benol; proof that benzene is halogen, nitro, cyano, CN6 alkyl, C1-C6 halo6 alkyl, C1-C6 alkoxy, and C1-C6 alkyl teo; 11 directions to 3 lifts;
A cation R'R5R that can be traced independently from the group consisting of a substituted phenyl group and a substituted benzyl group substituted with a valiant group;
Contains 'R7N'.

It should be appreciated that when R1 is hydrogen, the compounds of the invention may exist in any one of three tautomeric forms as shown below.

In the following margins, X includes halodane, nitro, cyano, C1-C alkyl, and 01-C6 alkoxy.

Appropriate R1μ hydrogen, benzoyl, benzene plate is substituted with 1 to 311 m1 substituents included from halogen, nitro, C-C alkyl, C1-C6 alkoxy and C1-C6 haloalkyl. substituted benzoyl, as well as groups M where M is an alkali gold ion.

Suitable R is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, benzyl and benzene, nitro, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkoxy. Includes benzyl substituted with 1 to 3 substituents.

Suitable R includes C1-C6 alkyl.

The uniform number n includes O or an integer traced from 1 to 3k.

A suitable m is an integer selected from 0 or 1 and 2.

Thana (Wrl, C1-C3 alkyl? Tomu.

D-IL x6 Halodane; Nitro; Cyano; Hydroxy; C1-C4 alkyl; C1-C4 alkoxy; C2
~C4ylkenyloxy; C4-C4 alkylthio; C
1-C4 alkylsulfinyl; C1-C4 alkylsulfonyl; formyl, C2-C6 alkanoyl and their oximes o-C1-C4 alkyl ether; C2-
C6 alkanoyloxy; bennoyloxy; sulfamoyl; N, N-)(C1-C4 alkyl)sulfamoyl; nitro, hydroxy, C1-C4 alkoxy and C
fCC1-C4 alkyl substituted with one substituent selected from the group consisting of 1-C4 alkylthio; C1-C substituted with one or more substituents selected from halogen;
4-alkoxy; a group in which R8 and R9 are independently selected from aqueous and C2-C4 alkanoyl; NR8R9;
C1 (2) q-, where q is an integer exclusive of 3 and 4.

Preferred RlC is aqueous; C2-C6 alkanoyl such as acetyl; benzoyl, benzene-valent cabalokene, nitro, C1-C6 alkyl, and 01-C6 alkoxy. Benzoyl substituted with 3 substituents; benzenesulfonyl as well as benzene monkey; 11 to 3 halogens, nitro, C4-C6 alkyl and 01-C6 alkoxy. Substituted benzenesulfonyl, a substituted benzene sulfonyl, which is considered a substituent; alkaline fluorescent cations such as lithium, potassium and sodium, alkaline earth metal cations such as magnesium, calcium and barium, manganese, pot, zinc , transition mTh cations such as iron, nickel, cobalt and iron, ammonium ions as well as tri- and tetra-(alkyl)ammonium ions where the alkyl is selected from C1-C6 alkyl and C4-C6 hydroxyalkyl. or organic canon; 1J.

Preferred R is C1-C6 alkyl; C2-C6 alkenyl; C2-C6 alkynyl; C1-C6 haloalkyno arch, C2-C6 haloalkenyl; and DC2-C6 haloalkynyl.

Preferably R includes C1-C6 alkyl.

0 and n are different integers from 1 and 2.

More preferred compounds of the invention include adducts of formula I, where n is 1, where Wl is methyl; ~C4 alkylthio, sulfamoyl, N
, N-)(C1-C4 alkyl)sulfamoyl, a group bridging two adjacent carbon atoms of a benzene monkey -(
CH2) from the group consisting of 3-; 1m monkey selected from nitro, halogen, methyl and methoxy
7% benzenesulfonyl substituted with k group, alkali metal canon, fluorine cation, ammonium ion, and alkyl is C1-C6 alkyl and C1-
Choose from C6 hydroxyalkyl! selected from the group consisting of tritrioles and tetra-(alkyl)ammonium ions; R=c, ~C3 full ion, C1-C3 alkyl, allyl and haloallyl; R = C1; ~
Return from C3 full kill; p is an integer from 0 or 1 to 3'X);
And m is the festival ridge drawn from 0 or 1 to 3. ) is a compound.

Among the more preferred compounds of the present invention are 4-indanyl compounds further substituted at the 7-position of the indanyl group. It can be traced independently from the pestle consisting of the formula (wherein W must be methyl; X and X7 are methyl, methoxy and ); different from the group consisting of metal canon; R'4; different from the group consisting of C1-C5 argyl, 2-haloethyl, allyl and 2-haloallyl; R3 is C
From 1 to C3 alkyl; p is O or 1 and 2
A pun is 7 and an integer; and m is an integer traced from 0 or 1 and 2. ) is a compound.

Also included among the most effective compounds of the present invention are 5-indanyl compounds loosely substituted at at least one of the 4- and 6-positions. That 1
independently selected from the formula (wherein W is methyl; X4 and X6 are aqueous, the group consisting of methyl, methoxy and halodane); at least one of X4 and X6 is not hydrogen; X7 is hydrogen, methyl , methoxy, halogen and N, N
-(methyl)sulfamoyl; RIU hydrogen, acetyl, nitrobenzoyl,
selected from the group consisting of methylbenzenesulfonyl and alkali metal cations; RUC, -C3 alkyl, 2-haloethyl, allyl and 2-haloallyl; R3 is selected from C-C alkyl; and 3 p is 0 or an integer greater than 1 and 2. ) is a compound of Ruru.

The compound that is even better between the two is the 4-indanyl L. /) ゐ. It has the formula Q (where X is selected from the group consisting of methyl, methoxy and halocarbon;
X7 is methyl; R1 is selected from the group consisting of hydrogen, acetyl, sodium and potassium; R2 is selected from ether and allyl; Hover over from propyl. ).

Among the more spectacular compounds among the more mysterious compounds is the 5-indanyl compound, which is further added to the 4- and 6-positions of the indan monkey.

- and - are independently selected from the group consisting of 6+-, where X4 and X6 are methyl, methoxy and -rodane; R1 is selected from the range consisting of hydrogen, acetyl, sodium and potassium; R1 is selected from the range consisting of hydrogen, acetyl, sodium and potassium; R2 is excluded from ethyl, allyl; and R3V unityl and n-propyl. I will be exposed. ) is a compound.

An example of a list of JG light compounds includes the compounds listed in Table 1a.

Table 1a Table 18 - Family 1a - Continuation Table 1b Table 1b - Continuation Table 1b Footnotes for Vc aC6H5CO b4-CI (3C6H4SO2 c Cf (2CHr = CH2 d4-NO2C6H4CO 6N(n-C4Kq )4 Table 1c Table 1d Table 1e Book The compounds of the invention can be prepared by a variety of methods, and in one aspect the invention provides a method for preparing compounds of formula I.

Advantageously, the surface transparency of the compounds of the invention can be considered in three or four parts.

Part A is 5-(substituted aryl)cyclohexane- of formula
Encompasses the 1,3-dione form X-. This reaction can be carried out in a two-step process, in which an aldehyde fatty conductor of formula (1) is condensed with acetone to form a ketone (2), which can be condensed with a malonic ester of formula (2). , either with or without isolation of the intermediate of formula ■, 5-(substituted aryl)cyclohexane-1 of formula ■
゜Give 3-dione.

Optionally, this preparation can be carried out in a two-step process by reacting an aldehyde fatty conductor of formula V with a malonic ester of formula Yes, it can be combined with an acetoacetate of formula .

In the process of 8 et al., this preparation is carried out by condensing a 2-aryl alkenoate derivative of formula XXI with an acetoacetate ester of formula X, with or without isolation of the intermediate of formula Either υ, 5- of formula ■
(Substituted aryl)cyclohexane-1,3-dione is provided.

The above gray areas and their order are shown below as part (1) of diagram A.

(11) and valence, where R is C
It represents a 1-C6 alkyl group.

Scheme A ■ (58) v vn (X)m XXI M■ Part B is a compound of formula ■ to give 2-acyl-3-(substituted aryl)-cyclohexane-1,3-dione of formula Xnl. Includes acylation of compounds. This reaction is expressed by the formula 5
This can be done by reacting -(substituted aryl)-cyclohexane-1,3-dione with:

(M Iikoshi of formula
(vll) a mixture of an acid anhydride of formula XV and a corresponding acid; (vll) a mixture of an acid halide of formula X■ and a corresponding acid;
(vi:o an alkali metal or alkaline earth metal hydride in which the reaction with an acid anhydride of formula XIV or an acid chloride of formula - reacting a 5-(substituted aryl)cyclohexane-1,3-dione of formula ■ with an acid halide of formula X■ in the presence of pyridine to give an acyl derivative; and then (x) an intermediate of formula X■ is incinerated with a Lewis acid catalyst; (x1) the intermediate of formula X■ is reacted with the corresponding acid of the acid halide of formula x■; or (X11) the intermediate of formula X■ is This can be done by reacting with imidazole.

Each of these reactions is outlined in Scheme B below, where hat is the halogen.

Below is the margin diagram B IX XIV ■x■ X■ (vl) IX XV ■ Xv (V*:1) IX XIV XV■
Xv Xv (x)

This reaction can be carried out by (xIii) reacting a compound of formula reacting a compound of formula XIII with hydroxylamine;
And, by reacting the adult oxime derivative with a formula alkyl-alizing agent to give a compound of formula (1), it can be ladled with either of the following formulas.

These reaction sequences are outlined in Scheme ○ below), where L is, for example, chloride, bromide, iodide, sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoro, hexafluoro Good dissociative groups such as phate, hexafluoroantimonate, methanesulfonate, fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate are described in Scheme C below.

Below is the blank diagram 〇(xr**)
can be prepared from compounds of the present invention having hydrogen, ie compounds of formula (1) and formula I, by any desired etherification, acylation or sulfonylation. This reaction is not schematically outlined below.

Below is the blank scheme D n XX ■ Formula 1 where R1 is an inorganic or organic cation? A compound of the present invention having a ll-sound can be produced from a compound of the present invention having the formula (■) in which R is hydrogen, that is, a compound of the formula (1), by reacting the compound of the formula (1) with an inorganic or organic salt. . For example, a compound of formula I in which R1 is an alkali metal ion can be prepared by reacting a suitable compound of formula (1) with a suitable alkali metal hydroxide or algoxylate by tl<-. can. Compounds of formula I in which R is a transferable fluorine ion or an active force f,in can be similarly prepared by reacting a compound with a suitable transferable metal salt or base. It's a monkey if you press it.

Compounds of A and I, where R is the same as the cation, and the ion is the same as the cation. -IR or alkali metal oxides can be prepared by reacting a suitable compound of formula I with a suitable fluorine salt or nanshin salt.

Therefore, the present invention further includes M, W, and X.

Provides a process for making compounds of formula I, where R, R, R, p, m and n are defined as MiJmlj, the process comprising:

a) Also reacting an aldehyde fatty conductor of formula V with acetone to give a ketone conductor of formula 2, and to give a 5-(substituted aryl)-cyclohexyl-7-1,3-cymene conductor of formula Then, the ketone spindle of the formula
Mr. Maron's enemy ester and anti-ia with C6 alkyl,
a; and e, to give the aryl methylane malonate tXy5 of formula ) Cyclohexane-1,3-dione conductor [- to give an arylmethylidene malonate conductor of formula X, wherein R is 01-C6 alkyl
or 5 of formula
-(kmenyl)cyclohexane-1,3-dione derivatives, the 2-arylalkanoate island conductor of formula XXI, where R is C1-C6 alkyl, is
- Reaction with acetoacetate of 2X which is C6 alkyl; b) 5 of formula -(Substituted phenyl)cyclohexane-1,3-dione derivative is converted into acid anhydride of formula X■ or formula x■
C) 2-acyl-3- of formula Xm to give compounds of the invention having formula
The 2-acyl of the formula When a -3-(full aryl)cyclohexane-1,3-dione derivative is reacted with hydroxylamine and the adult oxime intermediate is alkylized with an alkylating agent of formula XIX where L is preferably a leaving group, and optionally d) to give a compound of the invention having formula I:
Reacting the compound of the present invention having the formula with a compound of the formula where L is a good dissociative group, the formula ■, ■, lX, X,
I1. XX[, ■、■、■.

X, X11. XXl, Xll1. Novel compounds of XVI and n and processes for their preparation are provided.

The compound of formula (■) is active as a herbicidal agent and therefore the present invention is furthermore desirable.171'! A method for severely damaging or weeding plants, the method comprising applying an effective compound of formula I to the plant, i.e. the growth medium of the plant, as described above. provide.

Compounds of formula I are found in monocotyledonous weeds, wild grasses such as 1jL7.
It is active as a herbicide, particularly against wild grasses that are difficult to suppress in the harvest of cultivated plants. The compounds of the present invention are particularly useful in controlling wild grasses such as wild oats and cornstarch in cultivated monocot crops such as wheat, barley, and grains of the gods.

Therefore, the present invention provides a process for suppressing cotyledonous weeds in cereal crops such as wheat and barley, especially in cultivated crops, especially in wild grasses. The process is sufficient to severely damage or kill weeds, but not enough to substantially damage crops, as previously determined. X5. The compound of formula I can be applied to a crop, i.e. the growth medium of the crop. It becomes.

The compound of formula (II) may be applied directly to the plants (post-emergence application) or to the soil before the emergence of the plants (pre-emergence application). However, the compounds are generally more effective when applied after plant emergence.

The compounds of formula I can be used on their own for growth control, severely damaging or killing plants, but also when mixed with a carrier comprising a solid or liquid diluent. It can be used in the form of compositions comprising the compounds of the invention. Accordingly, from a further aspect, the present invention provides a plant growth inhibiting, plant damaging or herbicidal composition comprising a compound of formula (1) as defined above and a carrier inert thereto.

Certain compounds of formula (1) exhibit useful plant growth regulating activity. For example, while the compounds of formula (2) are selectively active herbicides against wild grasses in the harvest of cultivated plants at some application rates, they exhibit a disciplinary effect on plant growth in said harvest.

Plant growth regulating effects can be demonstrated in many ways. For example, suppression of apical eugenics, stimulation of auxiliary bud growth, stimulation of early flowering and seed formation, increased flowering and seed yield, shortening and dividing of stems. Plant growth regulating effects exhibited by compounds of the invention include, for example, tillering and stem shortening in crops such as wheat and barley.

Accordingly, one aspect of the invention further relates to a method for regulating plant growth, comprising applying to a plant, plant seed or plant growth medium an effective amount of a compound of formula I as defined above. To provide a method comprising:

To achieve the plant growth regulating activity 2 of the present invention, the compounds of formula I may be applied directly to the plants (post-emergence application) or to the seeds before (post-emergence) the plants or to the soil.

The compounds of formula I can be used on their own for the purpose of growing plants, but they are generally used in solid or liquid dilutions of 0 or 7! It is used in the form of a composition comprising a compound of the invention in admixture with a carrier containing r11.

Accordingly, it is still a further aspect of the present invention to provide a plant growth regulating active comprising a compound of formula (1) as defined above and an inert force carrier therefor.

The compositions of the present invention may be in solid, liquid or cast form. The compositions include both Inazawa compositions that are ready for immediate use and concentrated compositions that require dilution before use. The concentration of active ingredient in the compositions of the invention therefore depends on the type of formulation and whether the composition is amenable to use, e.g. as a fine powder formulation or as an aqueous emulsion, or whether the composition is suitable for e.g. dilution before use. This will vary depending on whether the concentrate is an emulsifiable concentrate or a wettable powder. Generally, the compositions of the present invention will comprise from 1 ppm to 99% by weight of active ingredient.

The solid compositions may be in the form of powders, dusts, islets, grits and granules in which the active ingredient is mixed with solid diluents. Powders and dusts can be prepared by mixing or milling the active ingredient with a solid carrier to give a finely divided composition. Granules, grits and pellets can be produced by binding the active ingredient to a solid carrier, for example by coating or impregnating a preformed granular solid carrier with the active ingredient, or by agglomeration techniques.

Examples of solid carriers are e.g. kaolin, bentonite,
Diatomite, Fuller's earth, Atakulay, Pore, Res, Talc, Stone powder, Dolomite, Limestone, Lime, Calcium carbonate, Powdered magnesia, Magnesium oxide, Magnesium sulfate, Ceracola, Calcium sulfate, Nonoirophyllite,
Mineral and clay such as silicic acid, silicates and silica gels; fertilizers such as Lun, ammonium acid, ammonium phosphate, ammonium nitrate and urea; such as coarse meal and flour, bark meal, wood meal, Natural products of biological origin, such as nut dust and cellulose powder; and synthetic polymeric materials, such as ground or powdered plastics and resins.

Optionally, the solid composition is such that the active ingredient and the solid carrier are wet enough to facilitate dispersion of the active ingredient in the liquid.
The species which act as emulsifying and/or dispersing agents may be in the form of dispersible or wettable dusts, powders, granules or granules in combination with more surfactants.

Examples of surfactants include cationic, anionic and nonionic types. Cationic surfactants include quaternary ammonium compounds, such as long chain alkyl ammonium salts such as cetyltrimethylammonium bromide. Anionic surfactants include soaps or alkali metal, alkaline earth metal, and ammonium salts of fatty acids; alkali metal, alkaline earth metal, and ammonium salts of lignin sulfonic acid; Naphthalene sulfonic acid salts, such as birnaphthalene sulfonic acid, salts of sulfonated naphthalenes and condensation products of naphthalene derivatives with formaldehyde, salts of sulfonated naphthalenes and condensation products of naphthalene derivatives with phenol and formaldehyde, and dodecylbenzene. alkali metal, alkaline earth metal, and ammonium salts of muarylsulfonic acids, including salts of alkylaryl pen-e sulfonic acids such as sulfonic acids; long chain monoesters of sulfuric acid or alkyl sulfates such as lauryl sulfate; and alkali metal, alkaline earth metal and ammonium salts of monoesters of sulfuric acid with fatty alcohol glycol ethers. Nonionic surfactants include condensation products of fatty alcohols such as oleyl alcohol and hisetyl alcohol with ethylene oxide; phenol and isooctylphenol condensation products of alkylphenols such as octylphenol and nonylphenol with ethylene oxide; castor oil and ethylene oxide; condensation products; partial esters derived from long chain fatty acids and hexitol anhydrides;
Examples include sorbitan monolaurate, as well as ethylene oxide and its condensation products; ethylene oxide/clopylene oxide glock copolymer; lauryl alcohol bilyglycol ether acetal; as well as hini lecithin.

Liquid compositions include a vinegar solution or dispersion of the active ingredient in a liquid carrier optionally containing one or more surfactants to act as wetting, emulsifying and/or dispersing agents.
i. Examples of liquid carriers are water; mineral oil fractions such as kerosene, bath naphtha, petroleum, coal tar oil and aromatic petroleum fractions; paraffin, cyclohexane, toluene, xylene, tetrahydronaphthalene and alkylated naphthalenes. 'Omachi Alizoku,
Cycloaliphatic and aromatic hydrocarbons; alcohols such as methanol, ethanol, chrononol, impropatol, butanol, cyclohexanol and hypropylene glycol; ketones such as cyclohexanone and isophorone; and dimethylformamide, for example. , dimethyl sulfoxide, N-methylpyrrolidone, and strong organic solvents such as sulfolane.

Preferred liquid compositions comprise an aqueous suspension, dispersion or emulsion of the active ingredient suitable for application by spraying, atomizing or pouring over water. Such aqueous compositions are generally prepared by mixing the concentrated composition with water.

Suitable concentrated compositions include emulsion concentrates, yeasts, oil dispersions, aqueous suspensions and wettable powders. The concentrate is usually diluted with water to form an aqueous formulation that will withstand long-term storage and will remain homogeneous for a sufficient period of time to permit application by conventional spray equipment after such storage. required to be possible. The concentrate is conveniently 2
It contains 0 to 99 parts by weight of active ingredient, preferably 20 to 60 parts by weight.

Emulsions or emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, conveniently containing one or more surfactants. Yeast can be prepared by blending the finely divided active ingredient with a finely divided solid carrier, one or more surfactants, and optionally an oil. Oil dispersions can be prepared by milling together the active ingredient, hydrocarbon oil, and one or more surfactants.

Concentrates of aqueous suspensions may conveniently be prepared by ball milling a mixture of the active ingredient, water, at least one surfactant and preferably at least one bar of suspending agent. Suitable suspending agents are, for example, hydrophilic colloids such as polyJ (N-vinylpyrrolidone), sodium carboxymethyl cellulose and the vegetable gums acacia and tracantho: montmorillonite, beidellite, nontronite, hectorite. , hydrated colloidal inorganic silicates such as hobosite, sauconite, and bentonite; and other ty) cellulose derivatives: and poly(vinyl alcohol). Wettable powder concentrates are prepared by blending together the active ingredient, one or more surfactants, one or more solid carriers, and optionally one or more suspending agents, and It can be conveniently manufactured by milling the mixture to provide a powder with the required particle size.

Aqueous suspension solutions, dispersions or emulsions may be prepared by adding surfactants and/or surfactants to the concentrate composition.
Or it can be made from a concentrate composition by mixing with water containing oil.

It is noteworthy that all compounds of the invention having formula 1 in which R1 is hydrogen are acidic.

The compounds of formula I may therefore be formulated and applied as salts with organic or inorganic bases. When the compounds of formula I are formulated and used in the form of their salts, the salt forms thereof, i.e. compounds of formula 1 in which R1 is an inorganic or organic cation, are used in the formulation. A compound of formula I that is hydrogen is used in the formulation and its salts can either be formed in the same reaction system by use of a suitable organic or inorganic base.

The method of application of the compositions of the invention depends to a large extent on the type of composition used and the ease of its application. Solid compositions may be applied by dusting or any other suitable means of scattering or scattering the solids. Liquid compositions may be applied by spraying, atomizing, splashing, dipping into irrigation water, or any other suitable means of dispersing or dispersing the liquid.

The rate of application of the compound of the invention may be determined, for example, by the compound selected for use, the nature of the plant whose growth can be inhibited by the formulation selected for use, and the amount of foliar or root uptake of the composition. It will depend on a number of factors, including whether it is applied to or not. As a general guideline, however, application rates of 90.005 to 2'Okg per hectare are appropriate, while application rates of 0.01 to 2'Okg per hectare are suitable.
It can be said that 5.0 kg is preferable.
In addition to one or more compounds of the invention, compositions of the invention may also comprise laf or more compounds of the invention that are not biologically active. For example, as noted above, the compounds of the present invention are generally substantially more effective against monocotyledonous or grass species than against dicotyledonous or broad-leaved species. As a result, in some applications herbicide use of compounds of the invention alone may not be sufficient to protect crops.

Thus, in an even more sophisticated embodiment, the present invention provides Af
There is provided a herbicidal composition comprising a mixture of at least one herbicidal compound of formula (1) as defined in Section J and at least one other herbicide.

The other herbicide may be any herbicide not in Formula 1. It will generally be a herbicide with complementary action. For example, one clever variety is a mixture containing herbicidal action against broad-leaved weeds. Another preferred class is that of mixtures containing contact herbicides.

Examples of useful supplemental herbicides include: A,
Benzo-2,1,3-thiacyanon-4-one-2,2- such as 3-isozolobylbenzo-2,1,3-thiacyanon-4-one-2,2-nooxide (common name bentazone) Dioxide: B, 4-1'rollo-2-methylphenoxyacetic acid (common name MCPA), 2-(2,
4-dichlorophenoquine) propionic acid (generic name dichlorzolop), 2.4.54-lichlorophenoxyacetic acid (generic name 2,4.5-T), 4-(4-chloro-2-
Methylphenoquino)butyric acid (common name VCPR), 2,4
-dichlorophenoxyacetic acid (common name 2,4-[)),
4-(2,4-dichlorophenogine)butyric acid (common name 2)
．． Hormonal herbicides such as 4-DB), 2-(4-chloro-2-methyl-phenoxy)propionic acid (common name mecocillob), and their derivatives (e.g. salts, esters, ryomides, etc.) and especially phenoxyalkalic Neu, phosphoric acid; C,3-44-(4-chlorophenoquine)phenyl)-
fx3-[4-(4-haophenoxy)phenyl] such as 1,1-trimethylurea (generic name: roloxuron)
-1,1-dialkylurea: D, 2-methyl-4
, 6-nonitrophenol (common name r)NOC'),
2-tert-butyl-4,6-sinitrophenol (generic name dinotab), 2-secondary-butyl-4
, 6-sinitrophenol (generic name: zonoseb) and its ester nonoceb acetate, nonitrophenol and its derivatives (e.g. acetate): E, N',
N'-diethyl-2,6-sinitro-4-trifluoromethyl-m-7enylenediamine (common name sinitroamine), 2,6-noni)0-N,N-dipropyl-4-
F, N'-(3, 4-dichlorophenyl)-N,N-dimethylurea (common name diuron) and N,N-)mef
Phenylurea herbicides such as RuN'-[3-(49fluoromethyl)phenyl]urea (common name fluoromellone); Phenyllupamoyl quinine phenylrupamates such as rupamate (generic name phemedizifam) and 3-[(ethquin-carbonyl)amine]phenylphenylcarbamate (generic name desmedifam); H, 5-7 mi/-4 to chloro 2-phenylpyridazin-3-one, such as -2-phenylhyridanone-3-one (generic name pyrazine); 1,3-cyclohexyl-5,6-)rimethyleneuracil (generic name lenacyl), 5-bromo -3-5ec-
Butyl-6-methyluracil (generic name: bromryocyl)
and uracil herbicides such as 3-tert-butyl-5-chloro-6-methyluracil (common name tert-acyl): J, 2-chloro-4-ethylamino-6-(iso-
propylamino)-1,3,5-trianone (generic name adrazine), 2-chloro-4,6-no(ethylamino)-1,3; 5-driason (generic name simazine) and 2-azido-4 Triazine herbicides such as -(iso-propylamino)-6-methylthio 1.3.5=trianone (common name aziprozothrin); Generic name Linuron), 3-(4-
Chlorophenyl)-1-methoxy-1-methylurea (
1-alcoquine-2 such as monolinuron (common name monolinuron) and 3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common name chlorobromulon)
-Alkyl-3-thenylurea herbicides: L, S-thiocarbamate herbicides such as S-propylnoderopylthiorubamate (common name perorate); M, 4-amino-4,5-dihydro-3-methyl-
6-phenyl-], , 2, 4-) Riryojin-5
-one (generic name metamitrone) and 4-amino-6-
N, 2.3.6-Trichlorobenzoic acid (common name 2.3
．． 6-TEA) 1,3,6-dichloro-2-methoxybenzoic acid (common name dicamba) and 3-amino-2,5-
Benzoic acid herbicides such as dichlorobenzoic acid (common name chlorampen): 0, N-butoxymethyl-α-chloro-2',6'
- diethylacetanilide (common name butachlor),
Corresponding N-methoxy compound (generic name alachlor)
, the corresponding N-iso-zorobyl compound el (generic name provacrol) and anilide herbicides such as 3Z4/-nochloroprobionanilide (generic name pro-gunil); P, 2,6-dichloro-benzonitrile ( Q. 2. Haloalkanoic herbicides such as 2-dichlorozolopionic acid (generic name Grapon), trichloro-acetic acid (generic name TCA) and their derivatives: R,4-nitrophenyl 2-nitro-4-) IJ Fluoro Methyl phenyl ether (generic name fluoronophen), methyl 5-(2,4-dichlorophenoquine)-2-ditropenzoate (generic name bifenox), 2-nitro-
diphenyl ether herbicides such as 3-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and 2-chloro-4-to1)fluoromethylphenyl 3-ethquin-4-ditrophenyl ether; 8, 2 -chloro-N-[(4-methquin-6-methyl-1,3,5-
N-(heteroarylaminocarbonyl) such as tria-non-2-yl)aminocarbonyl]benzenesulfonamide (commonly known as DPX 4189)
benzenesulfonamide; and T,N,N-dimethyl-diphenylacetamide (common name diphenamide), N-(1-naphthyl)phthalamic acid (common name naphthalam) and 3-ami, / -1,
2,4-) Other herbicides including lyazole.

Examples of useful contact herbicides include: U, those in which the active entity is 1,1'-tumethyl-4,4'-nobilinolium ion (common name Grafueto); Bibiritulium herbicides such as those whose entity is 1,1'-ethylene-2,2'-nobilinolium ion (common name diqueto); ■ monosodium methanearsonate (common name MSM
Organic arsenic herbicides such as A) and W,N-(phosphonomethyl)-glycine (common name glyphosate)
and its salts and esters.

The invention will now be illustrated, but not limited to, by the following example.

Example 1 (i) β-chlorozolopionyl chloride (71,9
L566 mmol) total aluminum chloride (75,5 g,
566 mmol) and ethylene dichloride (200 ml)
was added to the mixture. Add p-xylene (60
, 0g, 566 mmol) was added and the solution was stirred for 1υ at room temperature for 30 minutes and then poured into dilute hydrochloric acid. The organic phase was separated, washed with water, and dried over anhydrous sodium sulfate.

Evaporation of the solvent under reduced pressure gave a yellow oil, 2-(2-chloropropionyl)-2,4-dimethylbenzene, which was used immediately in the next step.

(11) Raw 2-(2-chloropropionyl)-1,4
-Dimethylbenzene was added to concentrated sulfuric acid (400 ml) and preheated at 7.105°C. The solution was then diluted with 10
Stirred at 5-110°C for 30 minutes.

The cooled mixture was poured onto crushed ice and the precipitate was collected to give 4,7-nomethylignol-1-one (59,4,!i', 656%) as a pale white solid, mp 70<0>C.

(110 zinc dust (25,0g), mercury chloride (2,5
g), concentrated hydrochloric acid (3ml) and water (50itl)'fr
Zinc amalgam "f!:4+7-" prepared by mixing together for 5 minutes and then decanting the aqueous solution
Nomethylingone-1-one (C25,09,156 mmol), acetic acid (5QmJ), water (50mg) and concentrated hydrochloric acid (
100 mg) was added to the mixture. The mixture was refluxed with vigorous stirring for 12 hours, then cooled, poured into water and extracted with diethyl ether. The ether extract was washed successively with water, diluted aqueous sodium bicarbonate solution, and water. It was then dried over anhydrous sodium sulfate and concentrated.

Purification by column chromatography (eluent hexane) over silica dal' (il- 4.7
- Nomethylindane (18.5 g, 814 units) was given.

The product is characterized by all-proton nuclear magnetic resonance spectroscopy,
The spectral data are listed in Table 2.

Example 2 The indane derivatives described in Table 2 were prepared following essentially the same procedure as described for Gold Side 1. Each product was characterized by proton nuclear magnetic resonance spectroscopy and all spectral data are listed in Table 2 below.

Below is a blank example 3 4,7-dimethylingone-1-one (6,00g, 38
mmol) (Example 1 (see D(++)) was dissolved in dimethylformamide (50 ml) and 60% sodium hydride (3.34 g: 76 mmol) was added portionwise over 10 minutes. The residue was stirred for a minute, then methyl iositoide (25 ml) was added in portions and stirring was continued overnight at room temperature. The mixture was poured onto crushed ice and extracted with diethyl ether. The ether extract was washed with water and anhydrous. Dry over sodium sulfate,
Further evaporation under reduced pressure gave a dark oil. Example 1,
As described in (iii), treatment of the oil with zinc chloride gave a colorless oil, which was purified by column chromatography over silica gel (eluent hexane) in 2,2. 4,7-titramethylidane (5.35 g, Section 809) was given. The product was characterized by all-proton nuclear magnetic resonance wavetroscopy, and the spectral data are listed in Table 3.

Example 4 The indane derivatives listed in Table 3 were prepared essentially following the same procedure as described in Example 3. Each product was characterized by proton nuclear magnetic resonance spectroscopy, and the spectral data are listed in Table 3 below.

Margin Example 5 This example details the production of green beans produced by a method directly analogous to that described in the literature.

Method A Indan f T F Wood and J Angioli
n+(Tetrahedron Letters r
1963 + 1) Furthermore, Far J Else
nbraun et al. (Journal of Organi
cChemistry, 31, 2716.1966). Each product was characterized by proton nuclear magnetic resonance spectroscopy, and the spectral data are all listed in Table 4 below.

Method B (+) Indanone f L I Smith et al. (J
our own of the American Che
mical 5ociety, 73 +3843.
It was prepared according to the general method described by (1951).

(11) We Parham et al. (Journa
l of the American 5ociety
(101) from the corresponding indanones according to the general method described by (1956) (1956). Each product was characterized by proton nuclear magnetic resonance spectroscopy, and the spectral data are listed in Table 4 below.

Method C (1) 3-phenylnoropion f'jHfr CKai
ser et al. (Journal of Medicinal
Chemistry + 23(5), 506.19
It was prepared according to the general method described by (80).

(11) Indanon fJ Koo (Journa
l of the American Chemical
5ociety + 75 + 181! L1953
) according to the general method described by
0 (110) indanones prepared from phenylpropionic acid were prepared from the corresponding indanones following essentially the same procedure as described in Example 1 (**o). Each product was characterized by proton nuclear magnetic resonance nitrile. The spectral data are also listed in Table 4 below.

The examples in the margins below detail the preparation of the indancarboxaldehydes of 2V used in the preparation of compounds of the invention having the formula T'c.

Method A: Indancarboxaldehyde was prepared by WFBeech et al.
Journal of the Chemical 5
society rl 954, PL297) and S
D Jolad et al. (Organic 5ynthes
was prepared from the corresponding aminoindan according to the general method described by J. Is, Vol 5 + P 139 ). The product was characterized by proton magnetic resonance spectroscopy, details of which are listed in Table 5 below.

Method B: Indancarboxaldehyde 1GAO1ah et al. (A
ngew, Chem, Int, FJd, 20
(10) +878.1981) from the corresponding bromoindanes. The product was characterized by proton magnetic resonance scattering, details of which are given in Table 5 below.

Method C゛Indancarboxaldehyde kAR1eche et al.
Organic 5 synthesis, Vol 5
It was prepared by direct formylation of the indane ring according to the general method described by + P 49 ). The product was characterized by proton magnetic resonance spectroscopy, details of which are given in Table 5 below.

Below in the margin Example 7 This example illustrates the trihydronaphthalenecarboxaldehyde of formula V used in the preparation of the inventive compound of formula I and hyhenzospelancal 74? The production of tuxaldehyde is described in detail. Cal? Soxaldehyde was also prepared following essentially the same procedure as described in Example 6. The product was characterized by all-proton magnetic resonance spectrum and the spectral details are given in Table 6 below.

The following margins are 8 (i) io% hydroxide) IJum water M'Q (5n ~
70m1)'r complete set 7 (50n+1ri and water (5[+
1') in bean-5-cal 7J? 2xaldehyde (18.50 g: 127 mmol) was added dropwise to the suspension over a period of 5 minutes. The mixture was heated to 65°C.
The mixture was stirred at a temperature of 11% for an hour and then extracted with dichloromethane (200 ml). The extract I was washed several times with water dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure using a rotary evaporator to give 1-(5-indanyl)budo 1- as a viscous oil. It gave en-3-one (19.25 g: 81%).

Proton magnetic resonance spectrum (CDCl2; δ (ppm))
:2.05(2H,m):2.35(3H,s'):
2.90 (4H, m): 6.62 (LH, d) near,
10-7.60 (4H, m).

(11) Diethylmalonate (17.5g: 110
1-(mmol) in absolute ethanol (5(III)) was added to a solution of sodium metal (1,91,9; 83 mmol) in absolute ethanol (5(III)) and the mixture was heated to reflux. 5-indanyl) Boudot 1
A mixture of -en-3-one (19.25 g: 103 mmol) was added over a total of 2 minutes and the mixture was heated under centrifugal flow for 2 hours. Aqueous solution of sodium hydroxide (3
0 solution, 5Q〃J) was added, and the mixture was further diluted with 1
Heated under distant current for V2 hours. The solution was diluted with water (200
ηtl) and the aqueous mixture was poured into ethyl acetate).
(2×100 lnl) twice. The aqueous phase was acidified with concentrated hydrochloric acid and heated gently with an ox until the evolution of carbon dioxide ceased. The aqueous mixture was extracted with ethyl acetate,
It was dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation. Product, 3-hydroxy-3-(5i
cyclohex-2-en-1-one as a white solid (18,70,!9; 79.6%), mp 198
It was cooled down to ℃.

Proton magnetic resonance spectrum (d6~nomethylsulfoxide; δ (ppm)): 1.80-3.80 (IIH.

m): 5.20 (IFl, s) near, 00-7.2° (3H, m): 11.8 (IH, wide S).

(iii) method fa) tsukoo methane (l Q Qml) te') Schiff (
3-hydroquine-3 in 1,74y; 22 mmol)
-(5-indanyl)cyclohex-2-ene-1~
A mixture of globionyl chloride (1,929: 22 mmol) was stirred at room temperature and at the same time
S rimole) was added dropwise over a period of 2 minutes.

Stirring was continued for 1 hour, after which the organic acid solution was diluted with anhydrous sulfuric acid.
) and the acid agent was removed under reduced pressure using a rotary evaporator. The resulting brown oil was immediately dissolved in 1,2-dichloroethane (50 #lI!') and the temperature was 30 °C. 3 at a speed not to exceed
Added dropwise over 0 minutes to a mixture of aluminum trichloride (5.85 g: 44 mmol) in 1,2-dichloroethane (50 ml). After stirring for 30 minutes at room temperature, the solution was poured into 100 ml of a 1:1 mixture of concentrated hydrochloric acid and water. The organic solution was passed through all anhydrous sodium sulfate, washed with dried water (2 x 200 ml), and the solvent was removed under reduced pressure using a rotary evaporator. The resulting yellow oil was purified by chromatography over silica dal (eluent dichloromethane) to give a yellow solid, mp 98°C, as 3-hydroxy-3-(51ngyl)-2,propionylcyclohexton-2-ene-1.
-one (1,71,9:27%) was given.

Proton magnetic resonance spectrum n, (CI”)C10:δ(p
pm) ) :1.10(3H,t) :2.00(2t
(, m): 2.50-3.40 (IIH, m) near, 0
0-7.40 (3H, m): 18.0 (LH, s).

(iii) Method (b) 3-Hydroxy-3-(5-indanyl)cyclohex-2-en-1-one (4,0,!9:18 mmol) was dissolved in propionic acid (4me) at 130°C under nitrogen. and propionic anhydride (4 nll). Eight drops of trifluoromethylsulfonic acid were added to the resulting clear solution and the mixture was stirred at 130° C. under nitrogen for a further IX/I 2 hours. The mixture was poured into water (500 InJ) and stirred for 4 hours (approximately 30 minutes) until all the acid and water reacted. The resulting solid was filtered, pumped to dryness, then dissolved in dichloromethane and purified by column chromatography on silica gel (eluent dichloromethane). 1′
3-hydroxy-3-(5-indanyl)-2-
Propionylcyclohex-2-en-1-one (1
, 88g: 37%), mp 98°C.

(110 Method (C) 3 Hydroxy-3-(5-indanyl)cyclohendi-2-en-]-one (4.0 g; 18.0 mmol) was dissolved in sodium hydride ( 60% W/W 0.80, 9:2
0.0 mmol) solution.

After 15 minutes, propionic anhydride (2,6,!+?: 2
0.0 mmol) and the mixture had a sound of 110 to 1
Heated at 20°C for 2 hours. Then it was mixed with water (300ml
) and diethyl needle (2X LOOml).
) was extracted. The ether extract was dried over anhydrous sodium sulfate and then evaporated under reduced pressure to give a yellow oil gold. Purification by column chromatography through silica gal (eluent dichloromethane) yields a yellow solid, mp 98°C as 3-hydroxy-3-(5-indanyl)-2-:/'Robionylcyclohex-2-
-en-1-one (2.76 g; 54 units) was given.

(iXA Ethoxyamine hydrochloride (0.42g:4
．． 1 mmol), then aqueous sodium 1 polyhydroxide (
17,0ml)i 3-Hydroxy-3-(5-indanyl)-2-propionylcyclohex-2-enone (1,10g) in absolute ethanol (200ml):
3.87 mlJ mol) of the solution.

The entire mixture was stirred for 4 hours at room temperature and then the ethanol was removed by evaporation under reduced pressure using a rotary evaporator. The entire residue was treated with dichloromethane and the organic phase was washed twice with dilute aqueous hydrochloric acid and twice with water. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by evaporation under reduced pressure to give the product, 2-C1-(ethoxyimino)propyl]-3, as a pale yellow oil.
-Hydroxy-3-(5-indanyl)-cyclohex-2-en-1-one (1.20 g: 94.8 thi) was obtained.

Characterizing the product by proton nuclear magnetic resonance spectroscopy;
The spectrum data is listed in Table 91, Example 30.

Example 9 Compound store 8, 9.10, 11, 12.13゜14.15
,16.19,20,21,22゜26.27,46.
47, 48, 52, 54 and 57 (see Tables 1a-1d)
were prepared from the appropriate aldehyde derivatives (see Examples 6 and 7) essentially following the same procedure as outlined in Example 8.

Each product was characterized by proton nuclear magnetic resonance spectroscopy and the spectral data are listed in Table 91, Example 30.

Example 10 (j) 2-Butyryl-3-hydroxy-3-(5-indanyl)cyclohex-2-en-1-one, yellow solid mp 92°C by methods (b) and (c) of Example 8 (111)
3-Hydroquine-3-(5-indanyl)cyclohex-2 following essentially the same procedure as described in )
- prepared from en-1-one and butyric anhydride.

(11) Yellow oil of 2-(1-(ethoxyimino)butyl]-3-hydroxy-3-(5-indanyl)-cyclohex-2-en-1-one Same procedure as described in All Examples 8Gψ was prepared from the hydrochloride salt of 2-butyryl-3-hydroxy-3-(5-indanyl)cyclohex-2-en-1-one and ethoxyamine in 86.1% yield essentially according to the following.Product All Proton Nuclei It was characterized by magnetic resonance spectroscopy and the spectral data are listed in Table 9, Example 30.

Example 11 Compound store 23.24,34,49,50,51゜53.
55, 56.58, 59.60 and 61 (ila and 1
b) by essentially following the same procedure as described in Example 10 to prepare 11% of the appropriate 3-hydroxy-3-device.
(indanyl) cyclohex-2-en-1-one (Example 28), butyric anhydride and the hydrochloride of ethoxyamine.

Each product was characterized by proton nuclear magnetic resonance spectroscopy and the spectral data are listed in Table 91 Example 3o.

Example 12 Compound shop 4, 6.39 and 44 (see Tables 1a and lb)
Example 8. Suitable 2-alkanoyl-3-hydroxy-5 essentially in accordance with the same procedures as described in (IV)
-(ffi-indanyl)cyclohex-2-dyn-1-one (see Example 29) and the appropriate hydrochloric acid ring conductor of the hydroxyamine. Each product was characterized by proton nuclear magnetic resonance spectroscopy, and the spectral data are listed in Table 92, Example 30.

Example 13 Sodium salt of 2-(1-(ethoxyimino)propylio3-hydroxy-3-(5-indanyl)cyclohex-2-en-1-one (2)z-[-(ethoxyimino)flovir]-3 -Hydroxy-3-(51danyl)cyclohexton-2-en-1-one (0,31
，! i': 095 mmol) in acetone (20 ml) and aqueous monovalent sodium hydroxide (3,8,d)
was added to some of the. The mixture totaled 10 at room temperature.
After stirring for a minute, the acetone was removed in a rotary evaporator under reduced pressure F. Toluene (50nL/)
was added and similarly removed by distillation. Two more aliquots of toluene are added and then distilled to give a pale yellow solid, mp <259'e as 2-(1-(ethoxyimino)glo'W''h ]-]3-hydroxy-3-5-indanyl)cyclohex Sodium 1' of 2-en-1-one was given.

Example 14 Compounds A 31 , 33 and 35 were prepared from compounds A 31 60 and 34 (see Table 1b) and sodium hydroxide following essentially the same procedure as described in Example 13. The product can be identified by its melting point listed in Table 91 Example 30.

Example 15 3-benzoyl-2-(l-(ethoxyimino)propyl]-3-(5-indanyl)-cyclohexno-2-
En-1-one (3) Space below 2-[1-(ethoxyimino)propylio3-hydroxy-3-(5-indanyl)cyclohex-2-en-one sodium salt (0.95 mmol) fc
Dissolved in acetone (501 nJ), benzoyl chloride (0.13?: 0.95 mmol) was added dropwise over 2 minutes. The mixture was stirred for 5 minutes at room temperature, then filtered and evaporated under reduced pressure to give 3-benzoyl-2-(l-(ethoxyimino)propyl)-
3-(5-indanyl)cyclohex-2-ene-1
-On (0,31f: 75.7 section) was given.

Characterize the product by proton nuclear magnetic resonance spectral
The vector data are listed in Table 9, Example 30.

Example 16 Compounds 32, 37, 38 and 42 were prepared by following the same procedure as described in Example 15.
7-drimethyl-4-indanyl)cyclohex-2
-ene-1-, prepared from sodium ti(31) and the appropriate acid chloride. Each product was characterized by proton nuclear magnetic resonance spectroscopy and the spectral data are shown in Table 9, Example 30 KM, ia! do.

Example 17 Copper salt (40) of 2-1(ff-toximino)butyl 3-hydroxy-3-(5',6
．． 7-) riftyl-4-indanyl)cyclohexton-2-en-1-one (61), (500t da, 1.31
mol) was dissolved in 7 ml of saturated acetic acid with 59 ml of copper. The mixture was then evaporated to dryness under total vacuum. The solid residue was washed successively with hot water, cold water and diethyl ether. , dried chestnut, pale green solid, mp2
2-(1-(ethoxyimino)zotyl) at 12℃
3-hydroxy-3-(5,6,7-)dimethyl-4-
The copper salt of indanylcyclohex-2-2-2-1-one (450 ml, 84 ml) was given.

Example 18 Compound A41 was prepared from Compound 61 following a procedure similar to that described in Example 17. The product was obtained as a solid and its melting point is reported in Table 9, Example 30.

Example 19 2-(1-(ethoxyimino)butylcou 3-hydroxy-5~(5°6.7-t!) in methanol (30d).
J methyl-4-indanyl) cyclohex x -2-x
A solution of lithium metal (9,0, 1.3 mmol) dissolved in methanol (2 mJ) was added to a solution of y-1-oy(61), (0,50jf: 1.3 mmol). . The mixture was stirred at room temperature for 15 minutes and then evaporated to dryness under reduced pressure to yield a colorless solid, mp<2s□°C.
as 2-C1-(ethoxyimino)zotyl]-3-hydroxy-3-(5゜6,7-) IJ methyl-4
1danyl) cyclohex-2-en-1-one (0
, 40y-: 78.0ti) was obtained.

Example 20 2-(1-(ethoxyimino)zotyl]-3-hydroxy-3-(5°6.7-dri'f-4-indanyl)cyclohex-2-en--one in methanol (5 ml) (0,63,P; 1.6 mmol) in a bath solution of tetra-n-butylammonium hydroxide (2,Q
+J) in 25 timethanol was added. The mixture was kept at room temperature for 3 hours and then rotary evaporated to 4? Dry under reduced pressure with a dryer 1#! evaporated to. residual 1
The snout was dissolved in dichloromecune (15 mJ) and water (15 m/). Separate the layers and remove the organic phase with water (2X1
0 m, A'), dried over anhydrous sodium sulfate and evaporated under reduced pressure as a yellow oil.
1-(ethoxyε)butyl-3-hydroxy-3
The tetrabutylammonium salt of -(5,6,7-1limethyl-4-indanyl)cyclohexton-2-en-1-one (0,56f) was obtained. It is timed by the production@all-proton nuclear magnetic resonance spectral, and its spectral data are shown in Table 9, f/1130.

Example 21 - Cyclohexton-2-en-1-one (17) (1)
5-(4,6-trimethyl-5-indanyl)-2-propionylcyclohexnor-2-en-1-one (1,55P; 4.8 mmol) in dichloromethane (12 mA') cooled to r<OC. , chlorosulfonic acid (5,
5IILl). The temperature was held at 0° C. for an additional 30 minutes, after which the mixture was allowed to warm to room temperature. The mixture was poured onto crushed ice and the organic phase was separated, dried over anhydrous magnesium sulfate and evaporated to give 5-(7-chlorosulfonyl-
4,6-nomethyl-5-indanyl)-3-hydroxy-2-propionylcyclo to give 2x-2-en-1-one (1,60/-; 81.0 ratio).

5-(7-chlorosulfonyl-4,6-,:,'methyl-3-(ntanyl)
-3-Hydroxy-2-propionylcyclohexton-2-en-1-one (1,60?; 3.9 mmol) was added. The reaction was stirred at '2o'c for 30 minutes and then allowed to reach room temperature. The mixture is acidified with gold tetrahydric acid,
5-(
(1,40)
:86.0%). The product was characterized by fc proton nuclear magnetic resonance spectroscopy and the spectral data are listed in Table 8, Example 29.

6 width 5-(4,6-nomethyl-7-N,N-trimethylaminosulfamoyl-5-indanyl)-2~C],
-(Ethoxyimino)zorovircy 3-hydroxy-
Example 80 of cyclohexton-2-en-1-one (17)
Following a procedure similar to that described in 5-(
4,6-nomethyl-7-N,N-trimethylaminosulfamoyl-5-indanyl)-3-hydroxy-2-7
'Robionyl's mouth was macerated from di-2-en-1-one. The product was characterized by proton nuclear magnetic resonance spectroscopy, and the vector data are provided in Table 9, Example 30.

Example 22 Compound A I 8 k Same procedure as outlined in Example 21 1
i@ from 5-(4,7-nomethyl-5-indanyl)-3-hydroxy-2-7'ropionylcyclohexnor-2-en-1-one (see Example 29). The product was characterized by proton nuclear magnetic resonance spectroscopy and the spectral data are listed in Table 9, Example 30.

Example 23 In 5-(6-chloro-4,7-dimethyl-5-indanyl)-3-hydroxycyclo, dis-2-ene-
1-one (see Example 28) (1,40, P: 4.8 mmol) was dissolved in ethanol (50 m) and water (2
Sodium bicarbonate (0,45?;0 ml) dissolved in
5.3 mmol) was added. The mixture was stirred until the evolution of carbon dioxide ceased, then all the solvent was removed under reduced pressure.

The dried solid was dissolved in dimethylformamide (50ml) and heated to 110°C.・Zometelformide (
Benzoic anhydride (1,19
y-: 5.3 mmol) was added and the mixture sound 1
The mixture was stirred at 10°C for 2 hours. The solvent was removed under reduced pressure and the residue was purified by column chromatography through silica sol (eluent dichloromethane) to give 2-benzoyl-3-(6-chloro-4,7) as a yellow oil.
23.
0chi) was given. Product Characterized by All-Proton Nuclear Magnetic Resonance Spectrum, Full Spectral Data Table 8, Example 29
Describe it in

(11) Following the same procedure as described in Example 8.0, 5-(6-chloro-4,7-nomethyl-5-indanyl)-2-[:1-(ethoxyimino) Bennortwo-3-hydroxy-cyclohetsuno2
-Prepared from the hydrochloride of en-1-one and ethoxyamine. The product was characterized by proton nuclear magnetic resonance spectrum and the spectral data are listed in Table 9, Example 30.

Example 24 Compound Oboro 45 was converted to 3-hydroxy-3-(5,6,7-drimethyl-4-indanyl)cyclo by a method similar to that described in Example 23, to di-2-en-1-one ( Example 28 (1ffl). The product 'fc1' was characterized by nuclear magnetic resonance spectroscopy and its spectral data are described in Example 30.

Example 25 1-one (7) (DI-(s, 6, 7, 8-tetrahydro-2-naphthyl)budo 1-en-3-one, recolor oil gold side 8, (as described in D) was prepared from 5.6.7.8-tetrahydro-2-nathaldehyde and acetone in 63% yield, essentially following the same procedure as 5.6.7.8-tetrahydro-2-nathaldehyde and acetone.

Proton magnetic resonance x-e vector (CDCl2; δ (ppm)
): 1.65 (4H, m): 2.30 (3H, ti
); 2.70 (4H, m); 6.60 (IH, d); 7
．． 00-7.30 (3H, m) near, 40 (LH, d)
.

(++) 3-hydroxy-3-(5,6,7,8-
Example 8 (++
48.) following essentially the same procedure as described in 48.).
1-(5,6,7,8-tetrahydro-2-
(naphthyl)-budo-1-en-3-one.

0il) 3-hydroxy-3-(5,6,7,8-
(tetrahydro-2-naphthyl) cyclohextcut-2-en-1-one (2,6?; 11.0 mmol) in dimethylformamide (lo1n/
) in sodium hydride (60 parts x 0.47
y-; 12.0 mmol) was added to the bath solution. The mixture was stirred under a barrier until a solution was obtained, the propionic anhydride was completely dissolved, and the mixture was heated to 120°C. The mixture was stirred at 120° C. under nitrogen for 2 hours,
The bath agent was then evaporated under reduced pressure. The mixture was treated with dichloromethane (20 ml) and the soluble portion of the residue was chromatographed over silica gel (eluent dichloromethane) to give 3-hydroxy-2-7° bionyl-3-(
26.2
%) as a yellow solid, mp 87°C.

(iV)2-[:1-(ethoxyimino)frovir]-
3-Hydroxy-3-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-2-1-one, yellow oil, unsuitable for the same procedure as described in According to the target, 57.3% yield, 3-hydroxy-
2-! Ropionyl-3-(5,6,7,8-tetrahydro-2-naphthyl)-cyclohex-2-ene-1-
It was prepared from the tetra-acid salts of 1 and hyethoxyamine.

The product is characterized by all-proton nuclear magnetic resonance spectroscopy,
The vector data are listed in Table 9, Example 30.

Example 26 Compounds A27.28 and 30 (see Table 1c) All 72
:3-hydroxy-3-(substituted 5.6.7.8-tetrahydro-1-naphthyl)cyclohex-2-2-1
-one (see Example 28) and the appropriate cardanic anhydride and ethoxyamine hydrochloride. Each product was characterized by proton nuclear magnetism 'K>, and the spectral data are listed in Table 9, Example 30.

Example 27 Compound 29 (see Table 1e)'t-3-Hydroxy-3
-(2,3,4-trimethyl-1-pencisperanyl)
-cyclohex-2-ene to 1-one (see Example 28)
, prepared from propionic anhydride and ethoxyamine hydrochloride.

The product is characterized by all-proton nuclear magnetic resonance spectroscopy,
The spectral data are listed in Table 9, Example 30.

Example 28 5-arylcyclohexane-1,3-phono 18 (+) and (11) of formula ■ used in the preparation of compound of formula ■
Follow the same steps as the one pirated in the book,
Prepared from appropriate aryl aldehyde derivatives.

Many of the 5-arylcyclohexane-1,3-nonones of formula (1) were obtained as solids and characterized by their nuclear magnetic resonance spectroscopy. For convenience, all proton nuclear magnetic resonance spectroscopy (PMR) data and/or melting point data are set forth in Table 7 below.

Margin below, ? , . 80ii) by acylation according to essentially the same procedure 1i as described in 80ii).
It was made from 3-dione derivatives.

2-acyl-5-arylcyclohexane-1,
Many of the 3-dione derivatives were obtained as oils and characterized by nuclear magnetic resonance spectroscopy. For convenience, all proton nuclear magnetic resonance spectroscopy (pHlr) data and/or melting point data are provided in Table 8 below.

Space below (153) Example 30 Many of the compounds of this invention are obtained as oils and can be characterized and identified by their nuclear magnetic resonance spectra. For convenience, proton nuclear magnetic resonance spectra (pm
r) Data and/or melting point data Example 31 This non-limiting example illustrates the preparation of formulations of compounds of the invention.

The compound, 4E = 61, is 74 V/V to give an emulsifiable concentrate 147 that can be diluted outside the desired concentration with water to form an aqueous emulsion that may be applied by spraying. [Teric, 1
N 13 and 3'ly v/v [Kemmat J
It was bathed in toluene containing 5C15B. (rT
cl is a trademark, [Terjc J N ] 3
It is an ethoxylation product of kenonylphenol: [K
emmat j is a trademark and “Kemmat ISC1
5B is a brand of calcium dodecylbenzenesulfonate. ) Compound &61. (5 parts by weight) and [Dyap
ol JPT (1 part by weight) [Terlc J N 8
(94 parts by weight) to yield a stable aqueous suspension that can be diluted with water to the desired concentration to give an aqueous suspension that can be applied by spraying. Don't grind Rumil. (rDyapol J is a trademark and “Dyapol J” is a trademark.
l, IPT is an anionic suspending agent; r Teri
c J N 8Id, ethoxylation product of nonylphenol. ) Compound A61 (10 parts by weight), [Ta
ric J N15 (5 parts by weight) and “Kemmat J
SC15B (5 parts by weight) was added to give an emulsifiable concentrate that could be diluted with water to the desired concentration to give an aqueous emulsion that could be applied by spray [5olvesso J 150 (
80 parts by weight). ("5olvesso J" is a trademark and "5olvesso J 150 is a high-boiling aromatic petroleum fraction.") d) Dispersible powder compound A61 (10 parts by weight), [Matexil J
DA/AC (3 parts by weight), "Aerosol J O'
r/B (1 part by weight) and China Clay 298 (86
parts by weight) were blended and then ground to give a powder composition having a particle size of less than 50 microns. ([Matexil
I is a trademark; [Matex order JDA/AC is the disodium salt of naphthalene sulfonic acid/formaldehyde condensate; [Aerosol J is a trademark;
Aerosol l O'r/B is a brand of dioctyl ester of sodium sulfosuccinate. ) Compound 7% 61 (99 parts by weight), silica aerodal (0.5 parts by weight) and synthetic amorphous silica (0.5 parts by weight) were blended and ground in a hammer mill to obtain a powder with a particle size smaller than 200μ. occured.

f) Dusting powder compound A61 (10 parts by weight), Ata Gurgite (1
0 parts by weight) and i+ilophyllite (80 parts by weight) were all thoroughly blended and then ground in a hammer mill,
This produces a powder with a particle size smaller than 2ooμ.

An emulsifiable concentrate and/or suspension of a compound of the invention is prepared essentially as described above in a), b) or C) and then prepared in water, optionally containing a surfactant and/or an oil. to give an aqueous composition of the desired concentration to be used (as described in Examples 32 and 33) for evaluation of pre- and post-emergence herbicidal activity of the compounds.

Example 32 The pre-emergent emasculating activity of compounds of the invention formulated as described in Example 31 was evaluated by the following method: A pusher with a test ridge was included in a seed box. in soil 2
Don't line up at the depth of crn. Chalcotyledonous and dicotyledonous seeds were sown in separate boxes and, after cutting, the two boxes were sprayed with the desired leaves of the composition of the invention. Two N seed boxes were made in the same manner but were not sprayed with the composition of the invention and were used for comparison. all ffi
Place in a glasshouse and lightly water with Overhead Sole to initiate germination, then water as needed for optimal tub growth. After 3 weeks the boxes were removed from the glasshouse 7 and the effect of the treatment was visually evaluated. As for the results, 0 represents 0-10 damage, ■ represents 11-30 damage, and 2 represents 31-30 damage.
60 represents damage, 3 represents 61-80tI) damage, 4 represents 81-99 damage, and 5 represents 100% damage.
Damage to plants is rated on a scale of 0 to 5 representing dead grass given in Table 10. Dalasi−←) means that the experiment was not performed.

The name of the test clay 1 is as follows: wh wheat Qt wild oat Rg dokumugi Jm Japanese millet P pea rp Ipomia Ms Karan (167) Example 33 A book formulated as described in Example 31 The herbicidal activity of the compounds of the invention after appearance was evaluated by the following method.

The chair containing the test seeds was placed in the soil contained in the seed box for 2 c.
They formed a line at a depth of rn. Seeds in separate seed boxes with duplicates for deuterots and dicots. Place 4 seed boxes in a glasshouse, water with an overhead sprayer to initiate germination, then water a little - as required for optimal plant growth. is. After the plants had grown to a height of approximately 10-12.5 crn, one box of each of the deuterots and dicots was removed from the glasshouse and sprayed with the desired I compound of the invention. If the spray was good, the boxes were returned to the glasshouse for an additional 3 weeks and the effect of the treatment was evaluated visually by comparison with the untreated control. The results are as follows: 0 represents 0 to 10 damage, 1 represents 11 to 30 damage, 2 represents 31 to 60 damage, and 3 represents 61 damage.
Plants are rated for plant damage in Table 11 on a scale of 0 to 5 where 80 represents damage, 4 represents 81 to 99 damage, and 5 represents 100 damage. A dash (-) means no experiment was performed.

The names of the test plants are as follows.

wh Wheat Ot Wild oats Rg Dokumugi Jm 8 millet P Pea rp Ipomia MS Karan Sf Sunflower or less margin (176) Example 34 The compound was added to Kl in methylchlorohexanone 21 per l
8I f-8panj80 and 782g per 1e “Tw
eenJ20 was formulated for testing by mixing the appropriate amount with 5 ml of an emulsion prepared by diluting 160 ml of the containing solution to 500 ml with water. [5
pan, 180 is the trademark for surfactants comprising sorbitan monolaurate.

[Tween J 201'I is a trademark for a surfactant comprising a condensate of sorbitan monolaurate with a 20 molar ratio of ethylene oxide. Each 5 ml emulsion containing the test compound was then diluted to 40 ml with water and sprayed on young bolted bee plants listed in Tables 12-13 below (post-emergence test). Trial 1
After 26 days, the damage to the sampled plants was evaluated as 1- on a scale of 0 to 9, where 0 is 0 to 1'04 damage and 9 is complete weed killing.

The extent of detergent damage was assessed by comparison with untreated control plants. The results are shown in Tables 12 and 13 below.
give to A dash ←) means the experiment was not performed.

Clothes 12 Compound dust 3 1 The names of the test plants were as follows.

Mz Corn Re Ricey Large Ct Cotton Sg Sorghum Ec Echinochloa Kurusu Gari (EEchn
ochloa crus-gall+) (Setari
a viridis sh Sorghum halepense Pm
Panieum maximum Sf Sunflower Table 13 The names of the test products were as follows.

Ww Winter wheat Br Spring barley Av Avena fat
ua) (179) B8 Bromus 5terilia LL Hosomugi Patent Applicant AIN-I Australia Limited Patent Attorney Agent T Ki Ki Patent Attorney Kazuyuki Nishidate Patent Attorney 1) Shin Patent Attorney Akira Yamaguchi (180) Continuation of page 1 Priority claim ■July 1982 2nd ■Australia (
AU) ■PF4686 0 Inventor Keith Joffrey Watson 36 29 North Maidway Street, Bocks Hill, Victoria 31, Australia 0 Inventor Graham John Bird 30 51 North Melbourne Alfred Street, Victoria, Australia 100 Inventor: Lindsay Nidwin Cross, Victoria, Australia 30 32 Meribailnong Middle Road, 658 [Phase] Inventor: Claem John Farquarson 30, 73 Reserve War Steane Street, Victoria, Australia 10

Claims (1)

[Claims] 1. Compounds having formula I. (wherein W may be the same or different and is selected from the group consisting of C4-C6 alkyl, C2-C6 alkenyl and UC2-C6 alkynyl; X may be the same or different) - Rodan; Nitro; Cyano; C1-C6 alkyl; nohelogne, nitro, hydroxy, C-C alkoxy and C4-6 C6 alkylthio; C2-C6 alkenyl; C2-C6
Alkynyl; Hydroxy; C1-C6 alkoxy; No1
C1-C6 alkoxy substituted with a substituent selected from C1-C6 alkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C2-C
6alkanoyloxy; (C1-C6 alkoxy)carbunyl; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; sulfamoyl; N-(C1-C6 alkyl)-sulfamoyl; N,N-so( C1-C6 alkyl) sulfamoyl; benzyloxy; benzene ring is halodane, nitro, C
1-C6 alkyl, C1-C6 alkoxy and C1-C
Substituted benoloxy substituted with 1 to 3 substituents selected from the group consisting of 6-haloalkyl; R8 and R9 consist of hydrogen, C-C alkyl, C2-6 C6 alkanoyl, benzoyl and benzyl The groups NRR, formyl and C2-C independently selected from the group
6-alkanoyl and their oxime, imine and Schiff base derivatives; and groups -(CH2), - bridging two adjacent carbon atoms of the benzene ring, in which q
is an integer selected from 2 to 5; R is hydrogen; C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 alkynyl;
C6 alkoxy, C1-C6 alkylthio, phenyl, hinibenzene, halogen, nitro, cyano, C1-C
6 alkyl, C1-C haloalkyl, C1-C6 alkoxy, and H6 C1-C6 alkylthio.
substituted phenyl substituted with 3 substituents, i-substituted c -c substituted with a substituent selected from the group consisting of
Alkyl; C4-C6 (alkyl) sulfonyl; benzenesulfonyl; benzene chloride, nitro, cyano, C-C alkyl, C1-, c66 haloalkyl, C-5-C alkoxy and C1-C6 alkylthio Substituted benzenesulfonyl substituted with 1 to 3 substituents selected from the group consisting of; acyl group;
and an inorganic or organic cation; R2 is C4-C6 alkyl; C2-C6 alkenyl;
2~C haloalkenyl; C2~C6 alkynyl; C2~
C6 haloalkynyl; alkyl group cahalogen, C1-C
6 alkoxy, C1-C6 alkylthio, phenyl, and benzene ring is halogen, nitro, cyano, C1-C6
Substituted phenyl substituted with 1 to 3 substituents selected from the group consisting of alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 argylthio,
Substituted C substituted with a substituent from the group consisting of
R3 is selected from the group consisting of C7-C6 alkyl; C1-C6 fluoroalkyl; C2-C6 alkenyl; C2-C6 alkynyl; and phenyl; p is 0 or 1 7'c integer selected from ~4 ;n
is 0 or an integer selected from 1-3; and m is 0 or an integer selected from 1-3. :2,
W may be the same or different, and 01 to C6
selected from the group consisting of alkyl, C2-C6 alkenyl and C2-c6 alkynyl; X may be the same or different, halo; nitro; cyano; C1-C6 alkyl; C6 alkoxy, and 01-C6
C1-C6 alkyl substituted with a substituent selected from the group consisting of alkylthio; C2-C6 alkenyl; C2-
C6 alkynyl; hydroxy; C1-C6 alkoxy;
C4-C6 alkoxy substituted with a substituent removed from halodane and C1-C6 alkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C-C alkanoyloxy; (C4-C6) alkoxydicarbonyl ; C-VC alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl;
Sulfamoyl; N-(C1-C6 alkyl)-sulfamoyl; One selected from the group of
substituted benzyloxy substituted with 3 substituents+,
R8 and R9 are hydrogen, C4-C6 alkyl, C2-C
6-alkanoyl, benzoyl and benzyl independently separated groups NRR, R selected from hydrogen and 01-C5 alkyl, where R is hydrogen, 01-C6 alkyl, phenyl, benzyl, hydroxy, C1-C6 a group selected from the group consisting of alkoxy, phenoxy and benoloxy -C(R10)=NR"; and a group PeCH which binds two adjacent carbon atoms of the benzene ring
2), -, where q is an integer selected from 2 to 5)
; R+t, s, hydrogen; C1-C6 alkyl; C2-C6 alkenino arch C2-C6 arginyl; alkyl group is 01-
C6 alkoxy, C1-C6 alkylthio, phenyl, and benzene ring is halogen, nitro, cyano, C1-C
6-alkyl, C-C haloalkyl, C1-C6 alkoxy and H-6 C1-C6 alkylthio, one or more
Substituted phenyl substituted with 3 substituents; C1-C
6(alkyl)sulfonyl; benzenesulfonyl; benzene ring is halogen, nitro, Schiff/, C to C alkyl,
Substituted benzenesulfonyl substituted with one to three substituents selected from the group consisting of C1-C6 haloalkyl, C1-C66 alkoxy and C1-C6 alkylthio; C2-C6 alkanoyl; Haroke 9n, Nitro, Cyano, C
1-C6 alkyl, C1-C6 haloalkyl, C1-C
1*-substituted benzoyl with one to three substituents formed from the group consisting of 6 alkoxy and 01-C6 alkylthio; 2-furoyl; 3-furoyl; 2-thenoyl; 3-thenoyl; Metal ions, alkaline earth metal ions, all transition group ions, and R, R, R and R are hydrogen; C1-C4 alkyl; the alkyl group is selected from the group consisting of hydroxy, halodane and C1-C6 alkoxy Substituted C1-C1o substituted with a substituent
Alkyl; Phenyl; Benzyl; Group-substituted phenyl and benzene ring traced from the radical consisting of halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 argylthio
An ammonium ion R4R independently selected from the group consisting of: a group-substituted benol substituted with 1 to 3 substituents;
an inorganic or organic cation selected from 5R6R7N; R2 is C1-C6 alkyl;
C2-C6 alkenyl; C2-C6 haloalkenyl; C
2-C6 alkynyl; C2-C6 haloalkynyl; alkyl group is halogen, C1-C6 alkoxy, 01-C6
Alkylthio, phenyl and benzene rings are halodane,
Nitro, cyano, C1-C alkyl, C-C haloalkyl, C1-C6 alco6 1
6 Substituted phenyl substituted with 1 to 3 substituents selected from the group consisting of xy and C1 to C6 alkylthio;
Substituted with a substituent selected from the group consisting of 0
selected from the group consisting of 1-C6 alkino arch; RidC-C alkyl; C4-C6 fluoroalkyl;
selected from the group consisting of 6 C to C fulkeninoarch C2 to C6 alkynyl;
or an integer selected from 1 to 3; and m is O or an integer selected from 1 to 3. 3. W may be the same or different and is selected from the group consisting of CN6 alkyl, C2-C6 alkenyl and 6 C2-C6 alkynyl; 0,fn1. =-) mouth, Schiff/; C1-C6 alkyl; 0 substituted with halogen, nitro or 01-C6 alkoxy
1 to C6 alkyl; C2 to C6 alkenyl; C2 to C alkynyl; hydroxy; C1 to C6 alkoxy; C to kTh with halokene or C1 to C6 alkoxy
C alkoxy; C2-C6 alkanoyloxy; 6 (C1-C6 alkoxy) carbonyl: C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C
6alkylsulfonyl; sulfamoyl; N-(C1~
C6 alkyl) sulfamoyl; N, N-so(C.~C6 alkyl) sulfamoyl; benzyloxy; benzene ring is halodane, nitro, 01~C6 alkyl, C
Substituted benoloxy substituted with 1 to 3 substituents selected from the group consisting of -C alkoxy and C1-C6 haloalkyl, R and R are hydrogen, C1-C alkyl, C2-C6 alkanoino the radicals NRR, formyl and C2-C independently selected from benzoyl and benol;
R1 is water; C1-C6 alkyl; C2-C6 alkenyl; C2-C6 alkynyl; C6 alkoxy, C1-C6 alkylthio, phenyl, benzene, nitro, cyano, C1-C6 alkyl, CN6 haloalkyl, C1-C6 alkoxy and h6 C1-C6 alkylthio. Substituted C-C alkyl substituted with a substituent directly substituted with a substituent; C1-C6 (alkyl) sulfonyl; benzene sulfonyl; ,
Substituted benzenesulfonyl substituted with 1 to 3 substituents selected from the group consisting of nitro, cyano, CN6 alkyl, C1-C6 haloalkyl, C-C alkoxy and 01-C6 alkylthio; C2-C6 alkanoyl; benzoyl and benzene rings are halodane, nitro, cyano, C1-C6 alkyl, C-C haloalkyl,
11-3 selected from the group consisting of C1-C6 alkoxy and C16-C6 alkylthio
Bennoyl; 2-furoyl; 3-furoyl; 2-thenoyl; 3-thenoyl substituted with any substituent;
Transition metal ion and R4゜R, R and R or hydrogen; C4
~C4° alkyl; substituted C4-C1o alkyl which is substituted with an alkyl group or a substituent selected from the group consisting of hydrogen, haloke9, and C4-C6 alkoxy; , nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl,
C1-C6 alkoxy groups substituted with 1 to 3 substituents selected from the group consisting of C4-C6 alkylthio; substituted phenyl and substituted benzyl;
C6 haloarkenino bow C2~C6 alquinino bow c2~C
6-haloalkynyl; alkyl group cahalogen, C1-C6
Alkoxy, C1-C6 alkylthio, phenyl and benzene salt or halogen, nitro, cyano, C1-C6
Substituted phenyl substituted with 1 to 3 substituents selected from m consisting of argyl, 01-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkylthio,
Substituted C substituted with a substituent from the group consisting of
selected from the group consisting of: 1-C6 alkyl; R'1dC4-C6 alkyl; C1-C6 fluoroalkyl; C2-C6 alkenyl; C2-C6 alkynyl;
and phenyl; p is 0 or an integer selected from 1 to 4; nl'
3. The compound according to claim 1 or 2, wherein i is 0 or an integer selected from 1 to 3; and m is 0 or an integer selected from 1 to 3. 4. X, which may be the same or different if more than one X is present, is selected from the group consisting of halodane, nitro, cyano, C4-C6 alkyl and C4-C6 alkoxy; is substituted with 1 to 3 substituents selected from the group consisting of aqueous benzoyl; benzene, nitro, C1-C6 alkyl, 01-C6 alkoxy, and 01-C6 haloalkyl. substituted benzoyl; a group M in which M is an alkali metal ion; selected from the group consisting of; R2c1-C6 alkyl; C-C alkenyl; C2-
6 C6 alkynyl; benol; and benzene bundle cabalodan, nitro, C-C alkyl, C1-C67/I/:1
R is selected from C1-C6 alkyl; p is 0 n is 0 or an integer selected from 1 to 3; and m is O or an integer selected from 1 and 2. Compounds described. 5. W is selected from 01-C3 alkyl; X may be the same or different,...rodane; nitro; cyano; hydroxy;
Alkenyloxy; C1-C4 alkylthio; C1-C
4-alkylsulfinyl; C1-C4 alkylsulfonyl; formyl, C2-C6 alkanoyl and their oximes o -C1-C4 alkyl I -thyl; C2-C
6-alkanoyloxy; benzyloxy; sulfamoyl; N, N--j(C1-C6 alkyl)sulfamoyl; substituted with &' with a substituent selected from the group consisting of nitro, hydroxy, C1-C4 alkoxy and C4-C4 alkylthio C4-C4 alkyl substituted with one or more substituents selected from halogen;
4-C4 alkoxy; a group NR8R9 in which R and R are independently selected from hydrogen and C2-C4 alkanoyl; and a group bridging two adjacent carbon atoms of the benzene ring -
(CH2), -, where q is an integer selected from 3 and 4; R1 hydrogen; C
2-C6 alkanoyl; benzoyl; substituted benzoyl whose benzene ring is substituted with 1 to 3 substituents selected from the group consisting of halogen, nitro, 01-C6 alkyl and C4-C6 alkoxy; benzenesulfonyl; benzene 1 to 3 rings from the group consisting of halogen, nitro, C1-C6 alkyl, and C1-C6 alkoxycara;
Substituted benzenesulfonyl substituted with two hydrogen groups: further alkali metal ion, alkaline earth metal ion, transition metal iA ion, ammonium ion and alkyl is C-C alkyl and C1-C6 hydroxyargyl or 6 an inorganic or organic cation selected from tri- and tetra-(alkyl)ammonium ions selected from the group consisting of;
2~C6 alkyninobow C1~C6 haloalkyl; C2~
C6 haloalkenyl; and C2-C6 haloalkynyl; R5 is selected from C1-C6 alkyl; p is O or an integer selected from 1-3; 3. A compound according to claim 1 or 2, wherein m is a selected integer; and m is an integer remote from 0 or 1 to 3. 6, Formula (W is methyl; xH halogen, C-C alkyl, 01-C4 alkoxy, C1-C4 alkylthio, sulfamoyl, N, N
-C(c,~C4alkyl)sulfamoyl, and a group bridging two adjacent carbon atoms of the hibenzene term-(
CH2)3-; R'hydrogen;acetyl;benzoyl; benzene term canitro; halogen;
Substituted benzoyl substituted with a substituent selected from the group consisting of methyl and methoxy; benzenesulfonyl; substituted benzene whose benzene ring is substituted with a substituent selected from the group consisting of nitro, halodane, methyl and methoxy Sulfonyl; alkali metal cation; transition metal cation; ammonium ion; and alkyl is C to C
tri- and tetra-(alkyl)ammonium ions selected from alkyl and C1-C6 hydroxyalkyl;
3 alkyl, 01-C3 haloalkyl, allyl, and haloallyl; R3 is selected from 01-C3 alkyl; p is 0 or an integer selected from 1-3; and m is 0 or 1-3. It is an integer selected from 3. ) The compound according to any one of claims 2 and 5. Formula 7 (wherein W is methyl; selected from; R1 is hydrogen; acetyl; benzoyl; substituted benzoyl substituted with a substituent selected from the group consisting of benzene ring, halokane, methyl and methoxy; benzenesulfonyl; benzene ring is nitro, halodane, methyl; substituted benzenesulfonyl substituted with a substituent selected from the group consisting of and methoxy; cations of alkali metals; cations of reduced metals; ammonium ions; selected from the group consisting of tri- and tetra-(alkyl)ammonium ions; R is C
Select from solutions consisting of 1-C3 alkyl, C1-C3 haloase11, aryl and haloaryl; R3 is C1
-C3 alkyl; p is O or an integer selected from 1-3; and m is 0 or an integer selected from 1-3. ) The compound according to claim 1.2, 3.5 or 6. 8, Formula (wherein X is from the group consisting of halokene, C1-C4 alkyl and C1-C4 alkoxy; R'B hydrogen y benzoyl; benzene salt is nitro, . . . Substituted benzoyl substituted with a substituent from the group consisting of;
selected from the group consisting of; R1dc1-C3 alkyl and allyl; R3 is removed from C4-C3 alkyl; and m is selected from O or 1 and 2; is an integer. ) The compound according to any one of claims 1 to 7. 9, Formula (wherein W is methyl; selected from the group consisting of the cations; R211 selected from the group consisting of C1-C3 alkyl, 2-haloethyl, allyl and 2-haloallyl;
traced from C3 alkyl; p must be O or an integer selected from 1 and 2; and m is O or an integer selected from 1 and 2. ) The compound according to any one of claims 1.2, 3, 5.6 or 7. Formula 10 (wherein W is methyl; x4H□x' is independently selected from the group consisting of hydrogen, methyl, methoxy and halogen, and at least one of X4 and X6 is not hydrogen; , methyl, methoxy, halodane and N, N-
)(methyl)sulfamoyl; R'lri selected from the group consisting of hydrogen, acetyl, benzoyl, nitrobenzoyl, methylbenzenesulfonyl and alkali metal cations; selected from the group consisting of 2-haloallyl; R3 is 01-
selected from C3 alkyl; and p is 0 or an integer selected from 1 and 2. ) The compound according to any one of claims 1 to 3 or 5 to 8. Formula 11 (wherein X5 is selected from the group consisting of methyl, methoxy and halogen; X6 is selected from the group consisting of hydrogen, methyl, methoxy and halogen; X7 is methyl; R1 is hydrogen, acetyl, sodium and selected from the group consisting of potassium; selected from R2N ethyl and allyl; and selected from R3N ethyl and n-globil. A compound according to any one of. 12, formula (wherein X4 and X6 are independently selected from the group consisting of methyl, methoxy and halogen; X7 is selected from the group consisting of hydrogen, methyl, methoxy and ... of potassium; R2 is selected from ethyl and allyl; and R3 is selected from ethyl and n-)° lobil; A compound according to any one of Items 8 to 10. 13,2-CI-(ethoxyimino)butylcy 3
-Hydroxy-3-(5,6,7-trimethyl-indan-4-yl)cyclohex-2-en-1-one; 3-acetyloxy-2-(l-(ethoxyimino)butyl)-3-( 5,6,7-dorimethyllindan-4-yl)cyclohex-2-en-1-one; 2-(1-(ethoxyimino)buteno1]-3-hydroxy-3-(5,6,7- 4limenaruindan-4-
2-[1-(ethoxyimino)f-ropyl]-3-hydroxy-3-(5,7-zomethyllindan-4-yl)cyclohex-2-en-1-one sodium salt; 2-en-1-one; and 5-(5-bromo-6,7-dimethyllindan-4-yl)-2-[:I-(ethoxyimino)-butyl]-3-
A compound according to any one of claims 1 to 3 or 5 to 7 in which the percentage is selected from the group consisting of hydroxycyclohexyl-2-en-1-one. 14. A compound having the formula ■ υ (in the formula, n, p and m are as described in any one of claims 1 to 5). (In the formula, n, p, m and R3 are those listed in any of the formulas 1HHI3 to 5:@t of %Tsukuba). 16. As the active ingredient, the percentage of the active ingredient is 5J.
J13. A weeding composition comprising a compound and a carrier for the same. 17. A method that severely damages unwanted plants or kills weeds, and does not apply any force within the range of effective bone removal requirements from item 1 to item 13. A method comprising applying a self-contained compound or an effective amount of the compound according to claim 1 16 to the plant or the body of the plant or the body. 18. A method for selectively controlling the growth of weeds in s:1'4 weeds in dicotyledonous crops using Ni, which is sufficient to damage or kill weeds. 18. The method of claim 17, comprising applying to the crop or the growth medium of the crop in an amount that is sufficient to substantially damage the crop, but insufficient to substantially damage the crop. 19. The method according to claim 18, which selectively suppresses the growth of monocot weeds in cultivated crops. 20. Claims 17 to 19 in which the formulation is applied at a rate ranging from 0.005 to 20 kli'/ha
The method described in any of the sections. 21. A method for synthesizing a compound of formula I according to any one of paragraphs 1 to 13JJ4, comprising: a) reacting a benzaldehyde conductor of formula (■) with acetone; 5-(substituted phenyl)- of formula (2) by reacting with a malonic acid ester of formula (2) to give a ketone derivative and in which the ketone barrier 'kR of formula (1) is C4-C6 alkyl.
To provide a cyclohexane-1,3-dione derivative; space below ■ b) Formula] to form a 2-acyl-3-(f-substituted phenyl)cyclooxane-1,3(
R3CO)20 R3COhatXIV
XVX■ C) 2-acyl-3-(okyakuphenyl)-cyclohexane-1,3-noone interstitial body τ of formula
and /”/r optionally diH2N0R2 A method comprising: providing a compound of the invention containing R'LXX.